Faster Excited-State Intramolecular Electron Transfer from Perylenediimide Dianion Compared to Its Radical Anion

Chao Lu; Kazuma Honda; Mamoru Fujitsuka

doi:10.1021/acs.jpca.4c05189

Faster Excited-State Intramolecular Electron Transfer from Perylenediimide Dianion Compared to Its Radical Anion

J Phys Chem A. 2024 Nov 21;128(46):9869-9875. doi: 10.1021/acs.jpca.4c05189. Epub 2024 Nov 8.

Authors

Chao Lu¹, Kazuma Honda¹, Mamoru Fujitsuka¹

Affiliation

¹ SANKEN (The Institute of Scientific and Industrial Research), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.

PMID: 39514891
DOI: 10.1021/acs.jpca.4c05189

Abstract

The properties of the excited perylenediimide dianion (PDI^2-∗) and its intramolecular electron transfer (ET) behavior were examined using femtosecond laser flash photolysis on PDI^2- and PDI^2--acceptor (A) dyads. Upon laser excitation, the dianion of PDI first generated a singlet (S₁) state, followed by a triplet (T₁) state. In all of the dyads, rate constants of the intramolecular ET from PDI^2-∗ (S₁) varied with the driving forces. Comparison of the PDI^2-∗-A and PDI^•-∗-A dyad systems revealed higher rate constants for the ET from PDI^2-∗ than from PDI^•-∗, which can be attributed to the difference in electronic coupling for the ET. These findings elucidate the previously unexplored photoinduced ET characteristics of PDI^2-, thereby advancing the groundwork for photochemical studies of excited multi-ions and their applications in related materials.